Acrylic Ester Polymers

Keywords

acrylic esters; 2-cyanoacrylic ester polymers

1 Acrylic Esters
Acrylic esters are represented by the generic formula

The nature of the R group determines the properties of each ester and
the polymers it forms. Polymers of this class are amorphous and are
distinguished by their water-clear color and their stability on aging.
Acrylic monomers are extremely versatile building blocks. They are
relatively moderate to high boiling liquids that readily polymerize
or copolymerize with a variety of other monomers. Copolymers
with methacrylates, vinyl acetate, styrene, and acrylonitrile are com-
mercially signiÞcant. Polymers designed to Þt speciÞc application
requirements ranging from soft, tacky adhesives to hard plastics can
be tailored from these versatile monomers. Although the acrylics
have been higher in cost than many other common monomers, they
Þnd use in high quality products where their unique characteristics
and efÞciency offset the higher cost.
The usage of acrylic esters as building blocks for polymers of
industrial importance began in earnest with the experimentation of
Otto Rohm. The Þrst recorded preparation of the basic building
block for acrylic ester polymers, acrylic acid, took place in 1843;
this synthesis relied on the air oxidation of acrolein. The Þrst acrylic
acid derivatives to be made were methyl acrylate and ethyl acrylate.
Although these two monomers were synthesized in 1873, their utility
in the polymer area was not discovered until 1880 when Kahlbaum
polymerized methyl acrylate and tested its thermal stability. To his
surprise, the polymerized methyl acrylate did not depolymerize at
temperatures up to 320°C. Despite this Þnding of incredibly high

Van Nostrand’s ScientiÞc Encyclopedia, Copyright © 2006 John Wiley & Sons, Inc. 1
thermal stability, the industrial production of acrylic ester polymers
did not take place for almost another 50 years.
The commercial discovery of acrylic ester polymers took place
while Otto Rohm was conducting his doctoral research in 1901.
Rohm obtained a U.S. patent in 1912 covering the vulcanization
of acrylates with sulfur. Commercial production of acrylic ester
polymers by the Rohm and Haas Co. of Darmstadt, Germany,
commenced in 1927.
To a large extent, the properties of acrylic ester polymers depend
on the nature of the alcohol radical and the molecular weight of the
polymer. As is typical of polymeric systems, the mechanical prop-
erties of acrylic polymers improve as molecular weight is increased;
however, beyond a critical molecular weight, which often is about
100,000 to 200,000 for amorphous polymers, the improvement is
slight and levels off asymptotically.
Under conditions of extreme acidity or alkalinity, acrylic ester poly-
mers can be made to hydrolyze to poly(acrylic acid) or an acid
salt and the corresponding alcohol. However, acrylic polymers and
copolymers have a greater resistance to both acidic and alkaline
hydrolysis than competitive poly(vinyl acetate) and vinyl acetate
copolymers.
Acrylic polymers are fairly insensitive to normal uv degradation
since the primary uv absorption of acrylics occurs below the solar
spectrum.
There are currently two principal processes used for the manufacture
of monomeric acrylic esters: the semicatalytic Reppe process and
the propylene oxidation process. The newer propylene oxidation
process is preferred because of economy and safety.
The toxicities of acrylic monomers range from moderate to slight. In
general, they can be handled safely and without difÞculty by trained
personnel following established safety practices.

1.1 Radical Polymerization

Usually, free-radical initiators such as azo compounds or perox-
ides are used to initiate the polymerization of acrylic monomers.
Photochemical and radiation-initiated polymerizations are also well
known. Methods of radical polymerization include bulk, solution,

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emulsion, suspension, graft copolymerization, radiation-induced,
and ionic with emulsion being the most important.
The vast majority of all commercially prepared acrylic polymers
are copolymers of an acrylic ester monomer with one or more
different monomers. Copolymerization greatly increases the range
of available polymer properties and has led to the development of
many different resins suitable for a broad variety of applications.
In general, acrylic ester monomers copolymerize readily with each
other or with most other types of vinyl monomers by free-radical
processes.
Acrylic ester polymers are used primarily in coatings, textiles, adhe-
sives, and paper.

2 2-Cyanoacrylic Ester Polymers

The polymers of the 2-cyanoacrylic esters, more commonly known
as the alkyl 2-cyanoacrylates, are hard glassy resins that exhibit
excellent adhesion to a wide variety of materials. The polymers are
spontaneously formed when their liquid precursors or monomers are
placed between two closely Þtting surfaces. The spontaneous poly-
merization of these very reactive liquids and the excellent adhesion
properties of the cured resins combine to make these compounds a
unique class of single-component, ambient-temperature-curing ad-
hesive of great versatility. The materials that can be bonded run the
gamut from metals, plastics, most elastomers, fabrics, and woods to
many ceramics.
The utility of these adhesives arises from the electron-withdrawing
character of the groups adjacent to the polymerizable double bond,
which accounts for both the extremely high reactivity or cure rate
and their polar nature, which enables the polymers to adhere tena-
ciously to many diverse substrates.
The cyanoacrylic esters are prepared via the Knoevenagel condensa-
tion reaction, in which the corresponding alkyl cyanoacetate reacts
with formaldehyde in the presence of a basic catalyst to form a low
molecular weight polymer. The polymer slurry is acidiÞed and the
water is removed. Subsequently, the polymer is cracked and redis-
tilled at a high temperature onto a suitable stabilizer combination
to prevent premature repolymerization. Strong protonic or Lewis

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acids are normally used in combination with small amounts of a
free-radical stabilizer.
Adhesives formulated from the 2-cyanoacrylic esters typically con-
tain stabilizers and thickeners, and may also contain tougheners,
colorants, and other special property-enhancing additives.
The 2-cyanoacrylic esters have sharp, pungent odors and are
lacrimators, even at very low concentrations. The TLV for methyl
2-cyanoacrylate is 2 ppm and the short-term exposure limit is 4 ppm.
Good ventilation when using the adhesives is essential.
Eye and skin contact should be avoided because of the adhesive’s
rapid tissue-bonding capabilities.
Both the liquid and cured 2-cyanoacrylic esters support combustion.
These adhesives should not be used near sparks, heat, or open ßame,
or in areas of acute Þre hazard. Highly exothermic polymerization
can occur from direct addition of catalytic substances such as water,
alcohols, and bases such as amines, ammonia, or caustics, or from
contamination with any of the available surface activator solutions.
Some of the market segments served by these versatile materials
include automotive, electronic, sporting goods, toys, hardware, mor-
ticians, law enforcement, cosmetics, jewelry, and medical devices.
The diverse nature of the cyanoacrylate adhesives applications illus-
trates vividly that there is no truly typical application. The number
of applications in which these adhesives are used is being expanded
daily as technological improvements continue to broaden their capa-
bilities.
Examples of some of the current uses for these adhesives include
retention of automotive gaskets, weather stripping, side trim, and
wiring harnesses; athletic shoes; swim masks; shotgun recoil pads;
arrow feathers; dolls and doll furniture; circuit board component
mounting and wire tacking; and lipstick tube and compact mirrors.
Medical devices include balloon catheters and tubing sets; the adhe-
sives are used by morticians to seal eyes and lips.

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Additional Reading

Billmeyer, F.W. Jr.: Textbook of Polymer Chemistry, Interscience

Publishers, New York, NY, 1957.
Caspary, W., and B. Tollens: Ann. 167, 241, 1873.
Coover, H. W., Dreifus, D. W., and O’Connor, J. T: in I. Skeist,
ed., Handbook of Adhesives, 3rd ed., Van Nostrand Reinhold Co.,
Inc., New York, NY, 1990, Chapt. 27.
Fr. Englehern, Berichte 13, 433, (1880); L. Balbiano and A.
Testa, Berichte 13, 1984, (1880).
Kahlbaum, G. W. A.: Berichte 13, 2348, 1880.
Lee, H. ed.: Cyanoacrylate Resins—The Instant Adhesives
Monograph, Pasadena Technology Press, CA, 1986.
Redtenbacher, J.: Ann 47, 125, 1843.
Riddle, E.H.: Monomeric Acrylic Esters, Reinhold Publishing
Corp., New York, NY, 1954.
U.S. Pat. 1,121,134 (Dec. 15, 1914), O. Rohm.